Metal oxides in lead-acid batteries

ABSTRACT

Disclosed is a lead acid battery having a negative electrode plate and a positive electrode plate, each plate formed of a lead-antimony grid coated with an active material. A separator is disposed between the first and second electrode plate faces and an electrolyte solution immersing the negative electrode plate, the positive electrode plate the separator. At least one of the lead-antimony electrode grids, the separator or the electrolyte solution contains TiO 2 , an amount sufficient to suppress the migration of antimony from the positive electrode plate to the negative electrode plate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No. 15/673,344 filed on Aug. 9, 2017, which claims the benefit of the filing date of U.S. Provisional Application No. 62/372,688, filed Aug. 9, 2016, entitled “Metal Oxides in Flooded lead-Acid Battery.” The entire content of these applications are hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to the chemical and electrical arts. In particular, this invention relates to the composition of the components of lead acid batteries.

Background of the Invention

A lead-acid battery includes a housing containing a positive electrode plate and a negative electrode plate. The electrode plates are typically formed of an electrode grid coated with an active material. While primarily constructed of lead, the electrode grids are often alloyed with antimony, calcium, or tin to improve their mechanical characteristics. Antimony is generally a preferred alloying material. The electrode plates are coated with active materials and separated by separator, all in contact with an electrolyte.

It is a drawback of such batteries that antimony may leach or migrate out of the positive electrode. Antimony deposition/poisoning of the negative plate leads to increased hydrogen evolution, electrolyte expenditure and loss of capacity and cycle life. Once the antimony deposits on the surface of negative electrode, it will change potential of negative electrode and cause the battery to be overcharged easily during application. This will undesirably shorten battery life.

One approach to overcoming the problem of antimony migration is to use a separator made of natural rubber. Rubber separators have improved functionality for deep cycle batteries with their antimony suppression feature. Rubber is often combined with a hydrated silica filler to introduce porosity to the rubber material.

Unfortunately, there are numerous drawbacks to the use of a natural rubber separator in addition to its expense. These drawbacks include poor integration of the hydrated silica filler producing pin-holes, low porosity, poor permeability and high electrical resistance. Furthermore, when the natural rubber separator is immersed in the acidic electrolyte of a lead-acid battery, it may oxidize and crack. When a rubber separator cracks, lead dendrites may grow from the negative to the positive electrode, thus causing the battery to short circuit.

Due to these drawbacks and to the expense of rubber, some manufacturers have abandoned the use of rubber altogether, instead, preferring to use a polymer separator for flooded lead-acid batteries. A polymer separator is much sturdier than a rubber separator, and thus does not tend to split when used in a flooded-lead acid battery. Such a polymeric separator may prevent the short circuits caused by lead dendrite growth, but does not suppress antimony migration. Thus, batteries using only a polymer separator have shortened battery life.

Consequently, there remains a long felt need for inexpensive lead acid batteries in which antimony migration has been suppressed. There remains a further long felt need for lead acid batteries having separators in which antimony migration has been suppressed and which possess desirable physical and mechanical properties.

SUMMARY OF THE INVENTION

Now in accordance with the invention, there has been discovered a lead acid battery that overcomes these and related disadvantages. The lead acid battery, which in one embodiment is a flooded lead acid battery, comprises a housing containing a negative electrode plate for a lead acid battery, the negative electrode plate having a first face, and a positive electrode plate for a lead acid battery, the positive electrode plate having a second face opposing the first face, where the electrode plates are comprised of a lead-antimony grid coated with an active material. A separator is disposed between the first and second electrode plate faces and an electrolyte solution, such as an H₂SO₄ solution, immersing the negative electrode plate, the positive electrode plate the separator. At least one of the lead-antimony electrode grids, the separator or the electrolyte solution contains TiO₂, which in some embodiments is Rutile TiO₂ or Anatase TiO₂, in an amount sufficient to suppress the migration of antimony from the positive electrode plate to the negative electrode plate.

In one aspect of the invention, the concentration of TiO₂ in the electrolyte solution is from about 0.1 to about 20 g/ml and, in some embodiments, the concentration of TiO₂ in the electrolyte solution is from about 0.25 to about 15 g/ml, while in some embodiments, the concentration of TiO₂, in the electrolyte solution is from about 0.5 to about 10 g/ml. In another aspect of the invention, at least one face of an electrode grid has a coating of TiO₂ with a thickness of from about 1 μm to about 10 mm and, in some embodiments, the TiO₂, coating has a thickness of from about 10 μm to about 1 mm, while in some embodiments, the TiO₂ coating has a thickness of from about 50 μm to about 500 μm. And in another aspect of the invention, the TiO₂ is incorporated into a porous membrane coated on the face of at least one electrode plate in an amount from about 1 to about 90 wt. % and, in some embodiments, incorporated into the porous membrane in an amount from about 10 to about 90 wt. %, while in some embodiments the TiO₂ is incorporated into the porous membrane in an amount from about 25 to about 75 wt. %.

In another aspect of the invention, the TiO₂ is incorporated into a polymeric separator in an amount from about 1% to about 50 wt. % and, in some embodiments, the TiO₂ is incorporated into the separator in an amount from about 5% to about 35%, while in some embodiments, the TiO₂ is incorporated into the separator in an amount from about 5 wt. % to about 25 wt. %. In still another aspect, the polymeric separator additionally includes natural rubber, RSS 1 or CV 60 rubber.

In still another aspect of the invention, the separator comprises a natural rubber separator and the TiO₂ is incorporated into the natural rubber separator in an amount from about 1 to about 40% wt. %. In some embodiments, the TiO₂ is incorporated into the natural rubber separator in an amount from about 1 to about 20 wt. % and, in some embodiments, the TiO₂ is incorporated into the separator in an amount from about 1 to about 10 wt. %.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, together with the specification, illustrate exemplary embodiments, and, together with the description, serve to explain the principles of these embodiments.

FIG. 1 is a partially cutaway perspective view illustrating a lead acid battery with electrodes in accordance with one aspect of the invention.

FIG. 2 is a partially cutaway front elevation view illustrating an electrode plate in accordance with one aspect of the invention.

FIG. 3 shows the effect of titanium dioxide powder in suppressing negative current caused by antimony migration.

FIG. 4 shows the effect of titanium dioxide leachate on reducing negative current caused by antimony migration.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

Particular embodiments of the invention are described below in considerable detail for the purpose of illustrating its principles and operation. However, various modifications may be made, and the scope of the invention is not limited to the exemplary embodiments described below. For example, while specific reference is made to flooded lead acid batteries, the invention is of equal use with other lead acid batteries, such as valve regulated lead acid batteries, including bi-polar lead acid batteries, AGM lead acid batteries and gel lead acid batteries.

FIG. 1 is a partially cutaway perspective view illustrating one aspect of a flooded lead acid battery in accordance with one aspect of the invention. The lead-acid battery 10 includes a housing 12 having positive and negative terminal posts 14 extending through the top of the housing to allow for electrical clamps to connect to the battery in operation.

A number of vertical partition walls 16 create a plurality of separate cell compartments 17. Each cell compartment contains a vertical stack of negative plates 18 and positive plates 20 having opposing faces spaced apart by separators 22 all immersed in an electrolyte solution 24 containing an electrolyte such as sulfuric acid (H₂SO₄).

Referring now to FIG. 2, there is shown a partially cutaway front elevation view illustrating one aspect of an electrode plate having coating with a porous, non-woven mat comprised of polymer fibers in accordance with one aspect of the invention. The negative and positive electrode plates 18, 20 are constructed with an underlying electrode grid 26. The electrode grid is primarily formed of lead-antimony alloy.

In one aspect of the invention, the electrode plates 18, 20 are formed by applying an active material paste 28 to the electrode grid 26. The positive and negative active material pastes generally comprise lead oxide (PbO) or lead (II). Suitable electrode plates are described in U.S. Pat. No. 8,546,006, which patent is herein incorporated by reference.

In another aspect of the invention, at least one face of an electrode plate 18, 20 is coated with a porous membrane 30. Suitable porous membrane-coated electrode plates are described in U.S. patent application Ser. No. 15/644,688, filed Jul. 7, 2017, which application is herein incorporated by reference.

And in another aspect of the invention, the separator 22 is formed of a suitable material. Suitable materials include, without limitation, polymeric materials, including polyolefins such as polyethylene, polypropylene, polybutylene, ethylene-propylene copolymers, ethylene-butylene copolymers, propylene-butylene copolymers, and ethylene-propylene-butylene copolymers;, as well as natural rubber materials.

In accordance with one aspect of the invention, there has been discovered lead acid batteries containing a metal oxide in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate. Titanium dioxide (“TiO₂”) being the presently preferred metal oxide. Useful forms of TiO₂ include both the Rutile and Anatase crystalline forms.

In one aspect of the invention, the metal oxide, such as TiO₂, is added directly to the electrolyte solution 24 in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate. In some embodiments, the concentration of metal oxide, such as TiO₂, in the electrolyte solution is from about 0.1 to about 20 g/ml, in some embodiments, the concentration of metal oxide, such as TiO₂, in the electrolyte solution is from about 0.25 to about 15 g/ml, and in some embodiments, the concentration of metal oxide, such as TiO₂, in the electrolyte solution is from about 0.5 to about 10 g/ml.

In another aspect of the invention, at least one face of an electrode grid has a coating of the metal oxide, such as TiO₂ in an amount sufficient to reduce or delay migration from the positive electrode plate to the negative electrode plate. In some embodiments, the metal oxide, such as TiO₂, metal oxide coating has a thickness of from about 1 μm to about 10 mm, in some embodiments, the metal oxide, such as TiO₂, coating has a thickness of from about 10 μm to about 1 mm, and in some embodiments, the metal oxide, such as TiO₂, coating has a thickness of from about 50 μm to about 500 μm. The coating can be formed by any suitable method.

In still another aspect of the invention, the metal oxide, such as TiO₂, is added to the active material applied to at least one negative electrode plate, at least one positive electrode plate or both at least one negative and at least one positive electrode plate in an amount sufficient to reduce or delay migration from the positive electrode plate to the negative electrode plate. In some embodiments, the metal oxide, such as TiO₂, is added to the active material in an amount from about 0.1 to about 5wt. %, in some embodiments, the metal oxide, such as TiO₂, is added to the active material in an amount from about 0.1 to about 2 wt. %, and in some embodiments, the metal oxide, such as TiO₂, is added to the active material in an a mount from about 0.1 to about 1 wt. %.

In still another aspect of the invention, the metal oxide, such as TiO₂, is incorporated into a porous membrane coated on the face of at least one electrode plate in an amount sufficient to reduce or delay migration from the positive electrode plate to the negative electrode plate. In some embodiments, the metal oxide, such as TiO₂, is incorporated into the porous membrane in an amount from 1 to about 90 wt. %, in some embodiments, the metal oxide, such as TiO₂, is added to the porous membrane in an amount from about 10 to about 90 wt. %, and in some embodiments, the metal oxide, such as TiO₂, is added to the porous membrane in an amount from about 25 to about 75 wt. %.

In another aspect of the invention, the metal oxide, such as TiO₂, is added to the separator. The separator can be made of any suitable material and includes separators made from polymers, natural rubber or combinations thereof.

In one aspect, the separator is a polymeric separator and the metal oxide, such as TiO₂, is present in an amount from about 1% to about 50 wt. %, In another aspect, the metal oxide, such as TiO₂, in an amount from about 5% to about 35% and in still another aspect, the metal oxide, such as TiO₂, in an amount from about 5 wt. % to about 25 wt. %, The TiO₂-containing polymeric separators suppress migration of antimony from the negative electrode plate to the positive electrode plate reducing hydrogen evolution, expenditure of electrolyte and reduction of battery capacity.

In another aspect of the invention, rubber material is integrated into the polymer separator. Suitable rubber materials, include without limitation is natural rubber, RSS 1 or CV 60 rubber. And in one aspect, the amount of rubber integrated into the polymer separator is from about 1 to about 40% wt. %, In another aspect, the amount of rubber is from about 1 to about 20 wt. % and in still another aspect, the amount of rubber is from about 1 to about 10 wt. %.

And in one aspect, the separator is a natural rubber separator and the metal oxide, such as TiO₂, is present in an amount from about 1 to about 50%, In another aspect, the metal oxide, such as TiO₂, in an amount from about 1 to about 25% and in still another aspect, the metal oxide, such as TiO₂, in an amount from about 1 to about 15%,

Example 1

TiO₂ powder added to a sulfuric acid electrolyte. Lead working electrodes were prepared by cutting lead wire (obtained from McMaster Carr—soft tempered bend-and-stay wire, 0.25″ diameter) into approximately 7 cm in length and insulating all except 13 mm on both ends of the wire using insulating tape. Counter electrodes were prepared the same way.

The working electrode, counter electrode and reference electrode (Hg/Hg₂SO₄) were placed into a 150 mL tall form glass beaker, along with 100 mL of sulfuric acid (1260 S.G.), ensuring that the exposed area of the electrodes were covered by electrolyte. The other exposed ends of the electrodes were connected to a potentiostat by attaching the black crocodile clip to the working electrode and the green crocodile clip to the reference electrode; while the red and white crocodile clips were attached to the counter electrode.

Conditioning cycles were run on the electrodes from −0.7 V to −1.8 V vs. Hg/Hg₂SO₄ for a number of cycles at a scan rate of 3 mV/s until a steady state was achieved (evident from the scans being superimposable on each other). Following the conditioning cycles, the electrodes were subjected to three cycles from −0.7 V to −1.2 V at a scan rate of 3 mV/s, after which the potential was stepped down to −1.2 V vs. Hg/Hg₂SO₄ and linear sweep voltammograms were obtained. The linear sweep voltammetry scans (LSVs) were obtained by initially holding the potential at −1.2 V vs. Hg/Hg₂SO₄ for 900 s (15 minutes), then sweeping the potential from −1.2 V to −0.7 V vs. Hg/Hg₂SO₄ at a scan rate of 3 mV/s (recording every 3 mV to reduce noise contamination). This was done three times for each solution; i.e., (1) blank solution (electrolyte only), (2) solution with added antimony, and (3) solution with antimony TiO₂ powder.

Titanium dioxide (500 ppm) powder was then added to 50 ppm antimony in 100 mL sulfuric acid electrolyte with a specific gravity of 1260 and LSV sweeps were performed. The effect of the titanium dioxide on reducing the negative current from addition of the antimony is shown in FIG. 3.

Example 2

A leachate TiO₂ is produced. The leachate is made by heating TiO₂ powder, in either Anatase and/or rutile crystalline form, in H₂SO₄ (1260 S.G.) at 70° C. for 72 hours. The concentration of TiO₂/H₂SO₄ amount is 10 g/100 ml. The components are placed in a round bottom flask with a water cooled condenser. After 72 hours the leachate is allowed to cool and remaining TiO₂ is filtered. The specific gravity (S.G). is adjusted to 1260.

LSV sweeps are performed as described in Example 1 where 10 ml TiO₂ leachate is added to 50 ppm antimony in 100 mL sulfuric acid electrolyte with a specific gravity of 1260. The effect of the TiO₂ leachate on reducing the negative current from addition of the antimony is shown in FIG. 4.

Without wishing to be bound by a theory of invention, it is believed that the addition of a metal oxide, such as TiO₂, reduces or delays antimony from poisoning the negative electrode and reduces the hydrogen evolution, leading to a longer battery life-time in lead-acid batteries where antimony-lead alloy grids are used. Poisoning of the negative electrode with antimony changes the potential of the electrode and as such, hydrogen evolution occurs easily, which dries out the battery and causes shortening of the lead-acid battery life.

It is believed that the metal oxide, such titanium dioxide, acts as an absorbent and/or leachate to bind antimony ions and inhibit the migration of antimony migration from the positive to negative plates In addition, the metal oxide, such titanium dioxide, improves the physical strengthening of separators made of polymer or natural rubber materials. As titanium dioxide absorbs to or complexes with antimony, it inhibits the antimony migrating to the negative electrode, poisoning it.

The addition of a metal oxide, such as TiO₂, eliminates the need for a rubber separator. Thus, the TiO₂ reduces the cost of the lead acid battery, by eliminating the need requirement for expensive antimony-suppressing rubber separators which are prone to splitting over time, creating electrical shorts through the battery and leading to end of battery life also. 

We claim:
 1. A lead acid battery comprising: a housing containing a negative electrode plate for a lead acid battery having a first face and a positive electrode plate for a lead acid battery having a second face opposing the first face, where the electrode plates are comprised of a lead-antimony grid coated with an active material; a separator disposed between the first and second electrode plate faces and an electrolyte solution immersing the negative electrode plate, the positive electrode plate the separator, where at least one of the lead-antimony electrode grids, the separator or the electrolyte solution containing TiO₂ in an amount sufficient to suppress the migration of antimony from the positive electrode plate to the negative electrode plate.
 2. The lead acid battery of claim 1 wherein the lead acid battery is a flooded lead acid battery.
 3. The lead acid battery of claim 1 wherein the TiO₂ is Rutile TiO₂ or Anatase TiO₂.
 4. The lead acid battery of claim 1 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.1 to about 20 g/ml.
 5. The lead acid battery of claim 1 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.25 to about 15 g/ml
 6. The lead acid battery of claim 1 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.5 to about 10 g/ml.
 7. The lead acid battery of claim 1 wherein the electrolyte is H₂SO₄.
 8. The lead acid battery of claim 1 wherein at least one face of an electrode grid has a TiO₂ coating in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 9. The lead acid battery of claim 8 wherein the TiO₂ coating has a thickness of from about 1 μm to about 10 mm.
 10. The lead acid battery of claim 8 wherein the TiO₂ coating has a thickness of from about 10 μm to about 1 mm.
 11. The lead acid battery of claim 8 wherein the TiO₂ coating has a thickness of from about 50 μm to about 500 μm.
 12. The lead acid battery of claim 1 further comprising a porous membrane coated on the face of at least one electrode plate, wherein TiO₂ is incorporated into the porous membrane in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 13. The lead acid battery of claim 12 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 1 to about 90 wt. %.
 14. The lead acid battery of claim 12 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 10 to about 90 wt. %.
 15. The lead acid battery of claim 12 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 25 to about 75 wt. %.
 16. The lead acid battery of claim 1 wherein the TiO₂ is incorporated into the separator in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 17. The lead acid battery of claim 16 wherein the separator comprises a polymeric separator and the TiO₂ is incorporated into the separator in an amount from about 1% to about 50 wt. %.
 18. The lead acid battery of claim 17 wherein the TiO₂ is incorporated into the separator in an amount from about 5% to about 35%.
 19. The lead acid battery of claim 17 wherein the TiO₂ is incorporated into the separator in an amount from about 5 wt. %% to about 25 wt. %.
 20. The lead acid battery of claim 17 wherein the separator further comprises natural rubber, RSS 1 or CV 60 rubber.
 21. The lead acid battery of claim 16 wherein the separator comprises a natural rubber separator and the TiO₂ is incorporated into the separator in an amount from about 1 to about 40% wt. %.
 22. The lead acid battery of claim 21 wherein the TiO₂ is incorporated into the separator in an amount from about 1 to about 20 wt. %.
 23. The lead acid battery of claim 21 wherein the TiO₂ is incorporated into the separator in an amount from about 1 to about 10 wt. %.
 24. An electrolyte solution for a lead acid battery, the lead acid battery having a housing containing a negative electrode plate, a positive electrode plate, the electrode plates comprised of a lead-antimony grid coated with an active material; a separator disposed between the first and second electrode plate faces and an electrolyte solution immersing the negative electrode plate, the positive electrode plate the separator, the electrode solution comprising: an electrolyte and TiO₂ in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 25. The electrolyte solution of claim 24 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.1 to about 20 g/ml.
 26. The electrolyte solution of claim 24 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.25 to about 15 g/ml.
 27. The electrolyte solution of claim 24 wherein the concentration of TiO₂ in the electrolyte solution is from about 0.5 to about 10 g/ml.
 28. The electrolyte solution of claim 24 wherein the electrolyte is H₂SO₄.
 29. An electrode plate for a lead acid battery, the lead acid battery having a housing containing a negative electrode plate, a positive electrode plate, the electrode plates comprised of a lead-antimony grid coated with an active material; a separator disposed between the first and second electrode plate faces and an electrolyte solution immersing the negative electrode plate, the positive electrode plate the separator, at least one face of an electrode grid comprising a TiO₂ coating in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 30. The electrode plate of claim 29 wherein the TiO₂ coating has a thickness of from about 1 μm to about 10 mm.
 31. The electrode plate of claim 29 wherein the TiO₂ coating has a thickness of from about 10 μm to about 1 mm.
 32. The electrode plate of claim 29 wherein the TiO₂ coating has a thickness of from about 50 μm to about
 500. 33. The electrode plate of claim 29 further comprising a porous membrane coated on the face of at least one electrode plate, wherein TiO₂ is incorporated into the porous membrane in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 34. The electrode plate of claim 33 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 1 to about 90 wt. %.
 35. The electrode plate of claim 34 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 10 to about 90 wt. %.
 36. The electrode plate of claim 34 wherein the TiO₂ is incorporated into the porous membrane in an amount from about 25 to about 75 wt. %.
 37. A separator for a lead acid battery, the lead acid battery having a housing containing a negative electrode plate, a positive electrode plate, the electrode plates are comprised of a lead-antimony grid coated with an active material; a separator disposed between the first and second electrode plate faces and an electrolyte solution immersing the negative electrode plate, the positive electrode plate the separator, the separator incorporating TiO₂ in an amount sufficient to suppress migration from the positive electrode plate to the negative electrode plate.
 38. The separator of claim 37 wherein the separator comprises a polymeric separator and the TiO₂ is incorporated into the separator in an amount from about 1% to about 50 wt. %.
 39. The separator of claim 38 wherein the TiO₂ is incorporated into the separator in an amount from about 5% to about 35%.
 40. The separator of claim 38 wherein the TiO₂ is incorporated into the separator in an amount from about 5 wt. % to about 25 wt. %.
 41. The separator of claim 38 wherein the separator further comprises natural rubber, RSS 1 or CV 60 rubber.
 42. The separator of claim 37 wherein the separator comprises a natural rubber separator and the TiO₂ is incorporated into the separator in an amount from about 1 to about 40% wt. %.
 43. The separator battery of claim 42 wherein the TiO₂ is incorporated into the separator in an amount from about 1 to about 20 wt. %.
 44. The lead acid battery of claim 42 wherein the TiO₂ is incorporated into the separator in an amount from about 1 to about 10 wt. %. 